Rem: Revista Escola de Minas ISSN: 0370-4467 [email protected] Escola de Minas Brasil Celino, Joil José; Corseuil, Henry Xavier; Fernandes, Marilda; Garcia, Karina Santos Distribution and sources of polycyclic aromatic hydrocarbons in the aquatic environment: a multivariate analysis Rem: Revista Escola de Minas, vol. 63, núm. 2, abril-junio, 2010, pp. 211-218 Escola de Minas Ouro Preto, Brasil Available in: http://www.redalyc.org/articulo.oa?id=56416596003 How to cite Complete issue Scientific Information System More information about this article Network of Scientific Journals from Latin America, the Caribbean, Spain and Portugal Journal's homepage in redalyc.org Non-profit academic project, developed under the open access initiative Joil José Celino et al. Geociências Distribution and sources of polycyclic aromatic hydrocarbons in the aquatic environment: a multivariate analysis (Distribuição e origem de hidrocarbonetos policíclicos aromáticos nos ambientes hídricos: uma análise multivariada) Resumo Joil José Celino Nesse trabalho, 14 dos hidrocarbonetos policíclicos aromáticos (HPA) Dr. em Geologia Regional incluídos pelo Environmental Protection Agency (EPA) na lista de poluentes Laboratório de Estudos do Petróleo prioritários foram analisados através de cromatografi a gasosa com espectrometria (LEPETRO) - Núcleo de Estudos de massas acoplada (GC-MS). A amostragem das águas superfi ciais foi realizada Ambientais (NEA), Instituto de no estuário do rio Paraguaçu e do rio Jaguaripe (Bahia), nordeste do Brasil. Geociências da UFBA (IGEO/UFBA) Concentrações totais de HPAs variaram de 0,0029 a 0,1079 ng/L em águas E-mail: [email protected] superfi ciais (rios principais, afl uentes), com valor médio de 0,0344 ng/L. Tais concentrações podem ser tomadas como valores-base para a região estudada. Os Henry Xavier Corseuil perfi s de HPAs foram dominados por HPAs de baixo peso molecular (dois ou Dr. em Engenharia Ambiental três anéis de componentes) em amostras de água superfi cial. Isto é indicativo de Laboratório de Remediação de sua origem a partir de óleo ou contaminação residual (entrada petrogênica). Os Águas Subterrâneas (REMAS) Departamento de Engenharia dados recolhidos mostram que entrada petrogênica foi predominante em quase Sanitária e Ambiental - Universidade todas as estações investigadas. Para discriminar diferenças e semelhanças entre as Federal de Santa Catarina (UFSC) amostras, a análise de componente principal (ACP) foi realizada utilizando uma E-mail: [email protected] matriz de correlação. A ACP revelou as relações entre todas as águas superfi ciais das estações investigadas. Marilda Fernandes Palavras-chave: Hidrocarbonetos policíclicos aromáticos (HPA), água superfi cial, Dra. em Química Analítica fonte, cromatografia à gás-espectrometria de massas (CG-EM), análise da Laboratório de Remediação de componente principal (ACP). Águas Subterrâneas (REMAS) - Departamento de Engenharia Sanitária e Ambiental - Universidade Federal de Santa Catarina (UFSC) Abstract E-mail: [email protected] Fourteen polycyclic aromatic hydrocarbons (PAHs) included in the US Environmental Protection Agency’s (EPA) priority pollutant list were analyzed Karina Santos Garcia using gas chromatography-mass spectrometry (GC–MS). Surface water sampling MSc. em Geoquímica e Meio was undertaken in the Paraguaçu Estuary (Bahia), northern Brazil. Total PAH Ambiente concentrations varied from 0.0029 to 0.1079 ng/L in the surface waters (main Laboratório de Estudos do Petróleo rivers, tributaries) with a mean value of 0.0344 ng/L. Such concentrations can (LEPETRO) - Núcleo de Estudos be taken as background values for the studied region. The PAH profi les were Ambientais (NEA), Instituto de dominated by low molecular weight PAHs (two- and three-ring components) in Geociências da UFBA (IGEO/UFBA) surface water samples. It indicated that PAHs in surface water may have its origin E-mail: [email protected] from oil or sewage contamination (petrogenic input). The collected data showed that petrogenic input was predominant at almost all the stations investigated. REM: R. Esc. Minas, Ouro Preto, 63(2): 211-218, abr. jun. 2010 211 Distribution and sources of polycyclic aromatic hydrocarbons in the aquatic environment: a multivariate analysis To discriminate pattern differences and similarities among The Paraguaçu Estuary, in the Maragojipe region, is the samples, a principal component analysis (PCA) was part of the Todos os Santos Bay, which covers an area of performed using a correlation matrix. PCA revealed the around 1200 km² (Figure 1); water depth reaches 6 m except latent relationships among all the surface water from the in navigation channels (9-11 m depth). The Paraguaçu and investigated stations. Jaguaripe estuaries are micro tidal environments and its Keywords: Polycyclic aromatic hydrocarbons (PAHs), surface hydrodynamics are controlled mainly by ocean fl ow (Leão water, source, gas chromatography-mass spectrometry (GC- & Dominguez, 2000). Water temperature distribution in the MS), principal component analysis (PCA). Paraguaçu Estuary, presents a warm season from December to March. Three main watersheds drain into the TSB, namely the 1. Introduction Paraguaçu, Subaé and Jaguaribe rivers (Figure 1), with long Water pollution by organic compounds, many of term average discharges of 112m³/s, 7.7m³/s e 0.32m³/s, which are known to be toxic or carcinogenic, has caused respectively (CEPLAB, 1979, Wolgemuth et al., 1981). The considerable and worldwide concern. Polycyclic aromatic fi rst two empty into the northern and western margins of the hydrocarbons (PAHs), hydrocarbons containing two or TSB, whereas the third debauches very close to the mouth of more fused benzene rings, are a group of ubiquitous organic the Itaparica Channel. These rivers probably have a minor pollutants of great environmental concern because of the impact on the oceanographic conditions inside the TSB (Lessa documented carcinogenicity in experiments with animals and et al., 2001). the widespread occurrence of several of its members (Manoli A majority of the surveys worldwide have been mainly et al., 2000). Due to their ubiquitous occurrence, recalcitrance focused on seawater (coastal of offshore) and estuarine water. and suspected carcinogenicity and mutagenicity, PAHs are However, little data is available for the PAH contamination of included in the U.S. Environmental Protection Agency (EPA) the inland waters of TSB, which usually acts as a receptor for and in the European Union priority lists of pollutants. The US sewage, industrial effl uents and urban or rural run off (Celino EPA fi xed 16 parent PAHs as priority pollutants, the latest & Queiroz, 2006). As streams and rivers, lakes and ponds being effective as of 1997 (Baumard et al, 1997; Mastral and are frequently used for potable water supply and water reuse Call´en, 2000; Magi et al., 2002; Szolar et al., 2002; Schubert is common, contamination of water sources is particularly et al., 2003). Some of these are considered to be possible or undesirable (Manoli & Samara, 1999). probable causes for human carcinogens and the endocrine disrupting activities of PAHs have been recently reported In Brazil, very limited studies for the monitoring of PAHs (Clemons et al., 1998; Brun et al., 2004). Therefore, their on surface water are performed (CETESB, 1979; CETESB, 1981; CETESB, 1990; CETESB, 2001; CRA, 2004). In order distributions in the environment and potential human health to evaluate the contamination status of PAHs in surface water risks have become the focus of much attention. from the estuarine region and aquatic environment, northern The Todos os Santos Bay (TSB), located in northeastern Brazil, an investigation has been performed with a quantitative Brazil, is the second largest coastal bay in the country GC-MS method. (Figure 1), after São Marcos Bay. The three main drainage basins convey an average of 120 m³/s of freshwater into the Bay, but majority of this fl ow has been hindered by a 2. Materials and methods dam in Paraguaçu River since 1985. The original average 2.1 Chemicals freshwater infl ow was two orders of magnitude smaller than the estimated tidal discharge through the main Bay entrance. Standard PAHs (16 compounds specifi ed on EPA Method The Bay’s oceanographic characteristics, as indicated by 610, each at 100, 200, 1000 or 2000ng/mL) in a mixture salinity measurements, are clearly marine (Lessa et al., 2001). were obtained from Supelco (Bellefonte, PA, USA). These The tides are semi-diurnal, and are amplifi ed up the Bay compounds are as follows: naphthalene (Np), metil-naphthalene by a factor of 1.5. Shallow water constituents become more (mNp), dimetil-naphthalene (dNp), acenaphthylene (Acy), important as the tide propagates along the Paraguaçu Channel acenaphthene (Ace), fluorine (F), phenanthrene (Ph), and Paraguaçu River, where they generate time asymmetries anthracene (An), fl uoranthene (Fl), pyrene (Py), chrysene that change between spring and neap tides. Currents are mainly (Chry), benzo[a]anthracene (BaAn), benzo[b]fl uoranthene bi-directional, and are stronger during the ebbing tide in most (BbFl), benzo[k]fl uoranthene (BkFl), benzo[a]pyrene (BaPy), of the Bay. Offshore, relatively strong tidal currents appear to benzo[g,h,i]perylene (B[ghi]Pe) and dibenzo[a,h]anthracene be felt in a radius of about 10 km, where they are superimposed (dB[ah]An). Internal deuteration standards for naphthalene-d8, on wind-driven currents orientated to the southwest (Lessa et acenaphthene-d10, phenanthrened10 and chrysene-d12